CN113784468B - Heating material and application thereof, conductive heating film and manufacturing method thereof - Google Patents
Heating material and application thereof, conductive heating film and manufacturing method thereof Download PDFInfo
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- CN113784468B CN113784468B CN202111064218.XA CN202111064218A CN113784468B CN 113784468 B CN113784468 B CN 113784468B CN 202111064218 A CN202111064218 A CN 202111064218A CN 113784468 B CN113784468 B CN 113784468B
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- 238000010438 heat treatment Methods 0.000 title claims abstract description 134
- 239000000463 material Substances 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 62
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 62
- 239000002002 slurry Substances 0.000 claims abstract description 62
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 18
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 51
- 238000004806 packaging method and process Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 16
- 238000005538 encapsulation Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000005087 graphitization Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- -1 naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride Chemical compound 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 6
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 23
- 239000007788 liquid Substances 0.000 abstract description 22
- 239000003822 epoxy resin Substances 0.000 abstract description 15
- 229920000647 polyepoxide Polymers 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 229920002521 macromolecule Polymers 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 87
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000003851 corona treatment Methods 0.000 description 10
- 229910021389 graphene Inorganic materials 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000000123 paper Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010336 energy treatment Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
Landscapes
- Surface Heating Bodies (AREA)
Abstract
The invention discloses a heating material and application thereof, a conductive heating film and a manufacturing method thereof, wherein the heating material is mainly prepared from the following substances in parts by mass: 0.8-1.2 parts of graphitized aqueous carbon nano tube slurry, 7-10 parts of aqueous acrylic resin or aqueous epoxy resin, 1-2 parts of deionized water and 0.001-0.01 part of high-molecular conductive dispersion liquid; the graphitized water-based carbon nano tube slurry is used, so that the heating and conductive performances of the graphitized water-based carbon nano tube slurry are more outstanding, the voltage required for converting electric energy into heat energy is lower, the highest voltage is 36V, the current is up to 14A, the graphitized water-based carbon nano tube slurry is safe and reliable, the consumed electric energy is less, and the energy is saved; and can also be directly combined with a solar power supply for use; the graphitized water-based carbon nano tube slurry is modified by the macromolecule conductive dispersion liquid, specifically, the activity of carbon element in the graphitized water-based carbon nano tube slurry is activated, so that the resistance of the graphitized water-based carbon nano tube slurry is increased.
Description
Technical Field
The invention belongs to the technical field of heating materials, and particularly relates to a heating material and application thereof, a conductive heating film and a manufacturing method thereof.
Background
The conductive heating film is a functional polymer material with wide application. In recent years, graphene (Graphene) is a two-dimensional carbon nanostructure material composed of single-layer graphite sheets, and has excellent mechanical and thermal properties. In particular, graphene can have mobility up to 2×10 4 cm 2 The resistivity of the graphene P [ mu ] m conductive and exothermic carbon film at room temperature can reach 108S/m, and the tolerance is 108A/cm 2 Is 100 times the copper withstand capability. Conductive and hair-developing graphene added with P [ mu ] mThe thermal carbon film can improve the conductivity in the conductive paste, and due to the advantages of inertia, low density and the like of the graphene, the addition of the graphene can improve the service life of the conductive paste and reduce the density of the paste, and the performance of the graphene can not meet the requirements of certain occasions, particularly relates to large-health and environment-friendly application although the graphene has the advantages.
Disclosure of Invention
Aiming at the problem that the existing graphene material can not meet the needs of certain occasions, the invention provides a heating material.
The invention adopts the following technical scheme: the heating material is mainly prepared from the following substances in parts by mass: 0.8-1.2 parts of graphitized water-based carbon nano tube slurry, 7-10 parts of water-based acrylic resin or water-based epoxy resin, 1-2 parts of deionized water and 0.001-0.01 part of high-molecular conductive dispersion liquid.
Further limited, the polymer conductive dispersion liquid is polymer carbon tube aqueous conductive dispersion liquid, and the graphitized aqueous carbon nanotube slurry is obtained by graphitizing the aqueous carbon nanotube slurry, wherein the graphitization degree is more than 90%.
The invention has the beneficial effects that: the graphitized water-based carbon nano tube is used, so that the heating performance is more outstanding, the voltage required for converting electric energy into heat energy is lower, the highest voltage is 36V, the current is up to 14A, the graphitized water-based carbon nano tube is safe and reliable, the consumed electric energy is less, and the energy is saved; and can also be directly combined with a solar power supply for use; the graphitized water-based carbon nano tube slurry is modified by the polymer water-based dispersion liquid, specifically, the activity of carbon elements in the graphitized water-based carbon nano tube slurry is activated, so that the resistance of the graphitized water-based carbon nano tube slurry is increased, and the heating performance is obviously increased; the heating material disclosed by the invention is simple in ingredients and environment-friendly.
The invention also provides a conductive heating film, which comprises a heating material layer, wherein the upper surface and the lower surface of the heating material layer are both fixed with packaging layers, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material.
Further defined, the surface of the heating material layer provided with the positive electrode and the negative electrode is integrally formed with the packaging layer.
Further defined, the packaging layer is made of one of plastic films such as PET substrate film, PE substrate film, TP μm substrate film, non-woven fabric and PI substrate film.
Further defined, one of the encapsulation layers is adhered with a release film/paper or protective film, which is far away from the heating material layer.
Further limited, the thickness of the packaging layer is 0.1mm, the thickness of the heating material layer is 40-80 mu m, and the thickness of the release film/release paper is 0.05mm.
The conductive heating film disclosed by the invention can be applied to the fields of industry and civilian use (automobiles, energy supply, construction technology, aviation and aerospace technology, machinery and equipment manufacturing, war industry technology, environmental protection technology and the like), indoor basic heating (walls, floors, ceilings), surface heating (seats, inner liners and the like) of automobiles, extension products (foot pads, clothes, mattresses, waist-protecting belts, eyeshields, seat cushions and the like), heating (molds and the like) in machinery and equipment manufacturing, medical fields (hose heating, sweat steaming rooms, thermotherapy apparatuses, warming devices and the like), special engineering heating (aerospace, war industry and the like), defrosting and the like; the temperature is fast, and the radiation is far lower than the safety standard; the waterproof performance is strong, and the service life is long; the heating is uniform in large area, and hot spots are avoided; the coating can be dried quickly after the coating is finished; the temperature reached by heating can be 20-450 ℃, and the temperature is controlled according to the requirement.
The invention also discloses a manufacturing method of the conductive heating film, which is characterized by comprising the following steps:
preparing a substrate film, a PET release film or a protective film, a copper foil electrode or a conductive silver paste electrode, graphitized water-based carbon nano tube paste, water-based acrylic resin or water-based epoxy resin, deionized water and macromolecule conductive dispersion liquid;
slitting the substrate film according to the width requirement, and carrying out surface corona treatment or precoating surface energy treatment;
dispersing and stirring graphitized aqueous carbon nano tube slurry, aqueous acrylic resin or aqueous epoxy resin and deionized water for 8-10 minutes by a stirrer of 300-500 rpm, adding high-molecular conductive dispersion liquid, dispersing and stirring, and activating carbon elements of carbon nano tubes by the high-molecular conductive dispersion liquid to obtain a heating material;
fixing one of the release film/paper or the protective film and the substrate film, and attaching the electrode to the rest of the substrate film;
coating a heating material on the substrate film attached with the electrode, and then drying;
and fixing the substrate film attached with the release film or the protective film with the heating material.
The beneficial effects of the invention are as follows: the manufacturing method is simple, time is saved, and the prepared conductive heating film has good performance.
The invention also provides a manufacturing method of the conductive heating film, which does not comprise a release film and comprises the following steps:
preparing a substrate film, an electrode, graphitized water-based carbon nano tube slurry, deionized water and macromolecule conductive dispersion liquid;
slitting the substrate film according to the width requirement, and carrying out surface corona treatment or precoating surface energy treatment;
dispersing and stirring graphitized water-based carbon nano tube slurry, water-based acrylic resin or water-based epoxy resin and deionized water for 8-10 minutes by a stirrer with the speed of 300-500 rpm, and then adding high-molecular conductive dispersion liquid for dispersing and stirring to obtain a heating material;
attaching the electrode to a part of the substrate film;
coating a heating material on the substrate film attached with the electrode, and then drying;
the remaining substrate film is fixed to the heat generating material.
The beneficial effects of the invention are as follows: the manufacturing method is simple, time is saved, and the prepared conductive heating film has good performance.
Drawings
Fig. 1 is a schematic diagram of the structure of a conductive heat generating film in embodiment 8;
fig. 2 is a schematic structural diagram of a conductive heat generating film in embodiment 9;
FIG. 3 is a graph showing the relationship between the surface resistance and the thickness of the heating material prepared in example 2;
fig. 4 is a schematic view of the conductive heat generating film prepared in example 11 and example 12;
wherein: 1-an encapsulation layer; 2-a heating material layer; 3-positive electrode; 4-a negative electrode; 5-release film.
Detailed Description
The heating material is mainly prepared from the following substances in mass: graphitized aqueous carbon nanotube slurry 100g to 2000g, preferably 500g, more preferably 1000g; 1kg to 10kg, preferably 6kg, of aqueous acrylic resin or aqueous epoxy resin, 1-2kg, preferably 2kg, more preferably 1kg, of deionized water; 1-10g, preferably 3-8g, more preferably 5g of the polymer conductive dispersion; wherein the graphitized aqueous carbon nanotube slurry can be obtained by graphitizing the aqueous carbon nanotube slurry described in the authority publication No. CN 103400991B; the high polymer conductive dispersion liquid is high polymer carbon tube water-based conductive dispersion liquid; the high-molecular conductive dispersion liquid activates carbon elements in graphitized water-based carbon nano tube slurry, so that the resistance of the graphitized water-based carbon nano tube slurry is increased, heating power is increased, the graphitized water-based carbon nano tube slurry has good heat conducting property, and hot spots are avoided; the voltage required by heating is low, safe and reliable, and can be applied to any fields requiring heat, such as medical treatment, military industry and construction, and finally can be applied to the field of battery shielding.
The conductive heating film comprises a heating material layer, wherein the upper surface and the lower surface of the heating material layer are both fixed with packaging layers, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material; the packaging layer can be made of a glass fiber board, paper leather, wood, a PVC substrate film, an organic acrylic board, a TP film, a PC substrate film and a PET substrate film, and is preferably a PET substrate film; both the positive electrode and the negative electrode can be made of copper foil or silver paste;
the surface of the heating material layer, on which the positive electrode and the negative electrode are arranged, is integrally formed with the packaging layer;
wherein, a release film is adhered to one of the packaging layers through an adhesive, the release film is far away from the heating material layer, the width of the layer formed by the adhesive is 35mm, and the thickness is 0.035mm; the thickness of the packaging layer is 0.1mm, the thickness of the heating material layer is 40-80 mu m, preferably 70 mu m, and the thickness of the release film is 0.025-0.188mm, preferably 0.05mm;
the number of layers of the heating film can be made into the required number of layers according to market demands, and the back of the release film or the back of the heating material layer is coated with a layer of water-based epoxy resin glue or water-based epoxy resin for waterproof treatment, so that the waterproof coating can be quickly adhered to different fields for use and waterproof application.
The manufacturing method of the conductive heating film comprises the following steps:
preparing a substrate film, a release film, an electrode, graphitized aqueous carbon nanotube slurry, aqueous acrylic resin or aqueous epoxy resin, deionized water and macromolecule conductive dispersion liquid, wherein the width of the substrate film is 900mm, the thickness is 0.1mm, and the preferable color is black;
slitting the substrate film according to the width requirement, and carrying out surface corona treatment, wherein the voltage in the corona treatment process is 1kv;
dispersing and stirring graphitized water-based carbon nano tube slurry, water-based acrylic resin or water-based epoxy resin and deionized water for 8-10 minutes by a stirrer with the speed of 300-500 rpm, and then adding the high-molecular conductive dispersion liquid to stir and disperse to obtain a heating material;
fixing the release film and the PET substrate film, and then attaching the electrode and the rest PET substrate film; after the electrodes are attached, the PET substrate film and the surfaces of the electrodes need to be cleaned synchronously, so that no dust and oil stains are ensured;
coating a heating material on the PET substrate film attached with the electrode, and then drying, wherein the drying temperature is correspondingly adjusted according to the thickness of the actual coating;
and (3) bonding the PET base material film attached with the release film with a heating material, wherein the bonding is realized by adopting aqueous epoxy resin glue.
A manufacturing method of a conductive heating film does not comprise a release film, and comprises the following steps:
preparing a substrate film, an electrode, graphitized aqueous carbon nanotube slurry, deionized water and macromolecule conductive dispersion liquid, wherein the width of the substrate film is 900mm, the thickness of the substrate film is 0.1mm, and the preferable color is black;
slitting the substrate film according to the width requirement, and carrying out surface corona treatment, wherein the voltage in the corona treatment process is 1kv;
dispersing and stirring graphitized water-based carbon nano tube slurry, water-based acrylic resin or water-based epoxy resin and deionized water for 8-10 minutes by a stirrer with the speed of 300-500 rpm, and then adding the high-molecular conductive dispersion liquid for dispersing and stirring to obtain a heating material;
coating a heating material on the PET substrate film attached with the electrode, and then drying, wherein the drying temperature is correspondingly adjusted according to the thickness of the actual coating;
and bonding the substrate film which is not bonded with the electrode with the heating material.
Example 1
The preparation of the heating material comprises the following steps:
s1: weighing the aqueous carbon nanotube slurry prepared in the example 1 in the authority publication number CN103400991B, and graphitizing the aqueous carbon nanotube slurry to obtain graphitized aqueous carbon nanotube slurry, wherein the graphitization degree is more than 90%; the graphitization method is not repeated in the present embodiment of the present method; the aqueous carbon nanotube slurry consists of the following substances in percentage by weight: 7.2% carbon nanotubes, 1.8% lithium salt of naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer and 91% deionized water; the naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer is prepared by polymerizing naphthalene acid, styrene sulfonic acid and maleic anhydride with a molar ratio of 1:1:1;
graphitized aqueous carbon nano tube slurry 0.8kg, aqueous acrylic resin 7kg, deionized water 1kg, aqueous conductive carbon black slurry 1g;
s2: and dispersing and stirring graphitized aqueous carbon nano tube slurry, aqueous acrylic resin and deionized water for 8 minutes by a stirrer of 300 revolutions per minute, and then adding aqueous conductive carbon black slurry, stirring and dispersing to obtain the heating material.
Example 2
The preparation of the heating material comprises the following steps:
s1: weighing the aqueous carbon nanotube slurry prepared in the example 1 in the authority publication number CN103400991B, and graphitizing the aqueous carbon nanotube slurry to obtain graphitized aqueous carbon nanotube slurry, wherein the graphitization degree is more than 90%; the graphitization method is not repeated in the present embodiment of the present method; the aqueous carbon nanotube slurry consists of the following substances in percentage by weight: 7.2% carbon nanotubes, 1.8% lithium salt of naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer and 91% deionized water; the naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer is prepared by polymerizing naphthalene acid, styrene sulfonic acid and maleic anhydride with a molar ratio of 1:1:1;
graphitized aqueous carbon nano tube slurry 1kg, aqueous epoxy resin 7kg, deionized water 1kg, aqueous conductive carbon black slurry 5g;
s2: and (3) dispersing and stirring the graphitized aqueous carbon nano tube slurry, the aqueous acrylic resin and deionized water by a stirrer at 400 rpm for 10 minutes, and then adding the aqueous conductive carbon black slurry for dispersing and stirring to obtain the heating material.
Example 3
The preparation of the heating material comprises the following steps:
s1: weighing the aqueous carbon nanotube slurry prepared in the example 1 in the authority publication number CN103400991B, and graphitizing the aqueous carbon nanotube slurry to obtain graphitized aqueous carbon nanotube slurry, wherein the graphitization degree is more than 90%; the graphitization method is not repeated in the present embodiment of the present method; the aqueous carbon nanotube slurry consists of the following substances in percentage by weight: 7.2% carbon nanotubes, 1.8% lithium salt of naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer and 91% deionized water; the naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer is prepared by polymerizing naphthalene acid, styrene sulfonic acid and maleic anhydride with a molar ratio of 1:1:1;
1.2kg of graphitized aqueous carbon nano tube slurry, 10kg of aqueous acrylic resin, 2kg of deionized water and 10g of aqueous conductive carbon black slurry;
s2: and (3) dispersing and stirring the graphitized aqueous carbon nano tube slurry, the aqueous acrylic resin and deionized water for 9 minutes by a 500-rpm stirrer, and then adding the aqueous conductive carbon black slurry for dispersing and stirring to obtain the heating material.
Example 4
The conductive heating film comprises a heating material layer, wherein the upper surface and the lower surface of the heating material layer are respectively fixed with a packaging layer, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material prepared in the embodiment 2; the packaging layer is made of PET substrate film; both the positive electrode and the negative electrode may be made of copper foil.
Example 5
The conductive heating film comprises a heating material layer, wherein the upper surface and the lower surface of the heating material layer are respectively fixed with a packaging layer, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material prepared in the embodiment 1; the packaging layer is made of PC substrate film; both the positive electrode and the negative electrode can be made of silver paste.
Example 6
The conductive heating film comprises a heating material layer, wherein the upper surface and the lower surface of the heating material layer are respectively fixed with a packaging layer, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material prepared in the embodiment 1; the packaging layer is made of PVC base material film; both the positive electrode and the negative electrode can be made of silver paste.
Example 7
The conductive heating film comprises a heating material layer, wherein the upper surface and the lower surface of the heating material layer are respectively fixed with a packaging layer, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material prepared in the embodiment 3; the packaging layer is made of PVC base material film; both the positive electrode and the negative electrode can be made of silver paste.
Example 8
As shown in fig. 1, a conductive heating film comprises a heating material layer 2, wherein an encapsulation layer 1 is fixed on both upper and lower surfaces of the heating material layer 2, a positive electrode 3 and a negative electrode 4 are arranged on the upper surface or the lower surface of the heating material layer 2, the surface of the heating material layer 2 provided with the positive electrode 3 and the negative electrode 4 is integrally formed with the encapsulation layer 1, and the heating material layer 2 is made of the heating material prepared in the embodiment 5; the packaging layer 1 is made of a PVC substrate film; both the positive electrode 3 and the negative electrode 4 may be made of silver paste.
Example 9
As shown in fig. 2, a conductive heating film comprises a heating material layer 2, wherein an encapsulation layer 1 is fixed on the upper and lower surfaces of the heating material layer 2, a positive electrode 3 and a negative electrode 4 are arranged on the upper surface or the lower surface of the heating material layer 2, the surface of the heating material layer 2 provided with the positive electrode 3 and the negative electrode 4 is integrally formed with the encapsulation layer 1, the other encapsulation layer 1 is adhered with the heating material layer 2 and a release film 5 by an adhesive,
the heat generating material layer 2 was made of the heat generating material prepared in example 2; the packaging layer 1 is made of PET substrate film; the positive electrode 3 and the negative electrode 4 may each be made of copper foil;
the width of the adhesive layer is 35mm and the thickness is 0.035mm; the thickness of the packaging layer 1 is 0.1mm, the thickness of the heating material layer 2 is 70 mu m, and the thickness of the release film 5 is 0.05mm.
Example 10
The conductive heating film comprises a heating material layer, wherein an encapsulation layer is fixed on the upper surface and the lower surface of the heating material layer, a positive electrode and a negative electrode are arranged on the upper surface or the lower surface of the heating material layer, the surface provided with the positive electrode and the negative electrode on the heating material layer is integrally formed with the encapsulation layer, and the other encapsulation layer is bonded with the heating material layer and the release film by an adhesive;
the heat generating material layer was made of the heat generating material prepared in example 2; the packaging layer is made of PET substrate film; both the positive electrode and the negative electrode may be made of copper foil;
the width of the adhesive layer is 35mm and the thickness is 0.035mm; the thickness of the packaging layer is 0.1mm, the thickness of the heating material layer is 55 mu m, and the thickness of the release film is 0.05mm.
Example 11
The preparation of the conductive heat generating film in example 10 specifically comprises the following steps:
s1: preparing a PET substrate film, aqueous epoxy resin, a release film/paper, a protective film, an electrode, graphitized aqueous carbon nano tube slurry, deionized water and high polymer conductive dispersion liquid, wherein the width of the PET substrate film is 900mm, the thickness of the PET substrate film is 0.1mm, and black is selected;
s2: cutting the PET substrate film according to the width requirement, and carrying out surface corona treatment, wherein the voltage in the corona treatment process is 1kv;
s3: dispersing and stirring graphitized water-based carbon nano tube slurry, water-based epoxy resin and deionized water for 8-10 minutes by a stirrer of 300 revolutions per minute, and then adding high polymer conductive dispersion liquid for dispersing and stirring to obtain a heating material;
s4: coating a heating material on the PET substrate film attached with the electrode, and then drying at 150-200 ℃;
s5: attaching the release film to another PET substrate film, and attaching by adopting an adhesive;
s6: the PET base material film attached with the release film is adhered with the heating material.
Example 12
The preparation of the conductive heating film in example 8 specifically comprises the following steps:
s1: preparing a PET substrate film electrode, graphitized water-based carbon nano tube slurry, water-based acrylic resin, deionized water liter and macromolecule conductive dispersion liquid, wherein the width of the PET substrate film is 900mm, the thickness is 0.1mm, and black is selected;
s2: cutting the PET substrate film according to the width requirement, and carrying out surface corona treatment, wherein the voltage in the corona treatment process is 1kv;
s3: dispersing and stirring graphitized water-based carbon nano tube slurry, water-based acrylic resin and deionized water for 8-10 minutes by a 500-rpm stirrer, and then adding the high-molecular conductive dispersion liquid for dispersing and stirring to obtain a heating material;
s4: coating a heating material on the PET substrate film attached with the electrode, and then drying at 150-200 ℃;
s5: and bonding the other PET substrate film with the heating material.
The heat-generating material prepared in example 2 was subjected to performance test, and the results are shown in table 1 and fig. 3.
TABLE 1
As is clear from table 1 and fig. 3, as the thickness of the coating layer increases, the resistance becomes smaller, and therefore the heat generation amount can be controlled by controlling the thickness of the coating layer, and other properties are also excellent.
In addition, as shown in fig. 4, the process apparatuses used in examples 11 and 12 were obtained by applying a heat generating material to a PET base film in screen printing and then baking the coated PET base film in an oven.
Finally, it should be noted that: the foregoing description is only of the preferred embodiments of the invention and is not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A heat generating material, characterized in that the method of preparing the heat generating material comprises the steps of:
s1: weighing aqueous carbon nanotube slurry, and graphitizing the aqueous carbon nanotube slurry to obtain graphitized aqueous carbon nanotube slurry, wherein the graphitization degree is more than 90%; wherein the aqueous carbon nanotube slurry consists of the following substances in percentage by weight: 7.2% carbon nanotubes, 1.8% lithium salt of naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer and 91% deionized water; the naphthalene sulfonic acid-styrene sulfonic acid-maleic anhydride polymer is prepared by polymerizing naphthalene acid, styrene sulfonic acid and maleic anhydride with a molar ratio of 1:1:1;
graphitized aqueous carbon nano tube slurry 0.8kg, aqueous acrylic resin 7kg, deionized water 1kg, aqueous conductive carbon black slurry 1g;
s2: and dispersing and stirring graphitized aqueous carbon nano tube slurry, aqueous acrylic resin and deionized water for 8 minutes by a stirrer of 300 revolutions per minute, and then adding aqueous conductive carbon black slurry, stirring and dispersing to obtain the heating material.
2. Use of the heating material of claim 1 in the fields of electromagnetic shielding, medical treatment, indoor heating, aerospace, military, foot pad, clothing, mattress, cushion, waist protection belt, eye shield, automobile, construction and environmental protection.
3. A conductive heating film, comprising a heating material layer, wherein the upper and lower surfaces of the heating material layer are both fixed with a packaging layer, the upper surface or the lower surface of the heating material layer is provided with a positive electrode and a negative electrode, and the heating material layer is made of the heating material of claim 1.
4. The conductive heat generating film according to claim 3, wherein the encapsulation layer is made of one of a PET substrate film, a PE substrate film, a release paper, a TP μm film, a nonwoven fabric, and a PI substrate film.
5. A conductive heat generating film according to claim 3, wherein one of the encapsulation layers is bonded with a release film or a protective film, which is remote from the heat generating material layer.
6. The conductive heat generating film according to claim 5, wherein the thickness of the encapsulation layer is 0.1mm, the thickness of the heat generating material layer is 40-80 μm, and the thickness of the release film is 0.05mm.
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